CN103928576B - SnS/ZnS overlapping thin film solar battery preparation method - Google Patents
SnS/ZnS overlapping thin film solar battery preparation method Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010409 thin film Substances 0.000 title claims abstract description 25
- 239000010408 film Substances 0.000 claims abstract description 111
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052786 argon Inorganic materials 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 13
- 238000005086 pumping Methods 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 35
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 17
- 238000001704 evaporation Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001755 magnetron sputter deposition Methods 0.000 description 7
- 238000007738 vacuum evaporation Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
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Abstract
The invention discloses a kind of SnS/ZnS overlapping thin film solar battery preparation method, belong to technical field of solar batteries.The method comprises the steps: a, is cleaned up by FTO electro-conductive glass, is installed on magnetron sputter substrate holder; B, unlatching vacuum-pumping system vacuumize; C, pass into argon gas, perform pre-sputtering program; D, again execution take out base vacuum; E, again pass into argon gas, when vacuum house vacuum degree reaches 2 ~ 9 × 10
-1after Pa, the shielding power supply opening SnS target prepares SnS film; ZnS film is prepared after SnS film preparation completes; F, repetitive operation, prepare 2 ~ 4 P-N junction altogether; Namely SnS/ZnS overlapping thin film solar battery is obtained after g, preparation Al film.The inventive method can improve cell light absorptivity, can improve cell photoelectric conversion efficiency, and preparation process is stable, temperature is low, energy consumption is low, is suitable for the application of large-scale commercial introduction.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of new SnS/ZnS overlapping thin film solar battery preparation method.
Background technology
SnS film is a kind of novel absorbing layer of thin film solar cell material, in natural P type semiconductor, can be combined into P-N junction with N type semiconductor ZnS, has nontoxic, that conversion efficiency is high feature.Prior art have two features, one is adopt vacuum evaporation technique in preparation technology; Two is on film solar battery structure, adopt single P-N junction structure.Application number 201010527964.3 " method of ZnS/SnS bilayer film is prepared in vacuum evaporation " has successfully prepared the thin-film solar cells based on " ZnS/SnS " P-N junction, this technical scheme adopts vacuum evaporation method, under vacuum conditions, by evaporation ZnS powder and SnS powder, prepare double-deck ZnS/SnS film at deposition on substrate one deck ZnS film and one deck SnS film.Due to inherent characteristic and the limitation of single P-N junction in absorb photons of vacuum evaporation technique, there is following shortcoming in this technical scheme: one is that deposition velocity is slow, and the migration of vacuum evaporation technique rete particle only relies on the concentration difference of rete evaporated material in vacuum chamber as actuating force; Two is that the particle energy that is evaporated is low, make the adhesion of film and substrate low, film easily comes off from substrate, particle can not move after arriving substrate surface well simultaneously, cause the final uniformity of film formed poor, for plural layers, make the interface between film not obvious, affect the performance of film function; Three is that the solid matter source of vacuum evaporation is point source, causes the uneven of forming thin film equally; Four is that vacuum evaporation technology can not accurately control, and beginning and the end of technique all need buffer time; Five is that evaporation is not suitable for large area and high speed plated film, is not suitable for modern industry and produces; Six is that evaporation can not accomplish continuous seepage, often produces a collection of, and all must repeat vacuum breaker-vacuumize-substance source premelt process, quality stability is poor; Seven is that single P-N junction bilayer film can not transform the photon absorbed in limit completely, and electricity conversion is restricted.Eight is that the program does not have back electrode metal level, is not complete solar cell.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of SnS/ZnS overlapping thin film solar battery preparation method improving absorptivity.
The technical solution adopted for the present invention to solve the technical problems is: SnS/ZnS overlapping thin film solar battery preparation method, comprises the steps:
A, the FTO electro-conductive glass as substrate to be cleaned up, be installed on magnetron sputter substrate holder; And then close magnetron sputter door for vacuum chamber after SnS target, ZnS target and Al target are installed;
B, unlatching vacuum-pumping system vacuumize, and make background vacuum reach 2 × 10
-3more than Pa;
C, unlatching argon inlet valve pass into argon gas, make vacuum degree in vacuum chamber reach 2 × 10
-1during Pa, open all target as sputter power supplys and perform pre-sputtering program;
After d, pre-sputtering EP (end of program), close all target power supplys, close argon inlet valve, again take out base vacuum to 2 × 10
-3more than Pa;
E, again unlatching argon inlet valve pass into argon gas, when vacuum house vacuum degree reaches 2 ~ 9 × 10
-1after Pa, the shielding power supply opening SnS target prepares SnS film, controls power density 100 ~ 300W/cm
2, sputtering time 10 ~ 30 minutes, film thickness 50 ~ 80nm; Prepare ZnS film after SnS film preparation completes, control power density 200 ~ 350W/cm
2, sputtering time 10 ~ 30 minutes, film thickness 50 ~ 80nm;
Prepare the program of SnS film and ZnS film in f, repeated execution of steps e, altogether prepare 2 ~ 4 P-N junction be made up of SnS film and ZnS film;
G, P-N junction have prepared rear preparation Al film, control power density 100 ~ 250W/cm
2, sputtering time 10 ~ 15 minutes, sputtering thickness 70 ~ 100nm, namely obtains SnS/ZnS overlapping thin film solar battery after Al film preparation completes.
Wherein, it will be appreciated by persons skilled in the art that vacuum degree described in the magnetron sputtering of this area or say that the above-mentioned vacuum degree essence of the present invention refers to the absolute pressure in certain space, 2 × 10
-3more than Pa essence refers to that absolute pressure is lower than 2 × 10
-3pa.
Wherein, in said method step a, the cleaning of FTO electro-conductive glass is cleaned under Ultrasonic Conditions with deionized water, acetone, absolute ethyl alcohol successively.
Wherein, in said method step c, pre-sputtering program setting for from build-up of luminance to the setting power time be 10 minutes, arrive after setting power and maintain 30 minutes.
The invention has the beneficial effects as follows: because the present invention adopts the mode of magnetron sputtering to prepare thin-film solar cells, the strict condition controlling each step of sputtering, and after pre-sputtering, again perform the program of taking out base vacuum, make film and basal body binding force stronger, be not easy to come off, and film forming is even, improves the absorptivity of thin-film solar cells; Magnetron sputtering can be accomplished to maximize, and pipelining high-speed and continuous is produced; The solar cell that in addition prepared by the present invention has 2 ~ 4 P-N junction be made up of SnS film and ZnS film of superposition, further increases the absorptivity of battery, namely can provide photoelectric conversion efficiency.The inventive method preparation temperature is low, energy consumption is low, speed is fast, is suitable for industrial production, is suitable for applying on a large scale.
Embodiment
SnS/ZnS overlapping thin film solar battery preparation method of the present invention, specifically comprises the steps:
A, the FTO electro-conductive glass as substrate to be cleaned with deionized water, acetone, absolute ethyl alcohol successively under Ultrasonic Conditions, be installed on magnetron sputter substrate holder after cleaning up; And then close magnetron sputter door for vacuum chamber after SnS target, ZnS target and Al target are installed.
Clean under Ultrasonic Conditions with deionized water, acetone, absolute ethyl alcohol successively, that substrate can be cleaned is more clean, and thoroughly the impurity of removing substrate surface, improves the adhesion of plated film rear film and substrate, prevent film from coming off from substrate surface.
B, unlatching vacuum-pumping system vacuumize, and make background vacuum reach 2 × 10
-3more than Pa.
It is to remove foreign gas in vacuum chamber and steam, avoiding foreign gas and steam on the impact of follow-up magnetron sputtering that this step vacuumizes.
C, unlatching argon inlet valve pass into argon gas, make vacuum degree in vacuum chamber reach 2 × 10
-1during Pa, open all target as sputter power supplys and perform pre-sputtering program; Pre-sputtering program setting for from build-up of luminance to the setting power time be 10 minutes, arrive after setting power and maintain 30 minutes.Thus make target reach operating state.
After d, pre-sputtering EP (end of program), close all target power supplys, close argon inlet valve, again take out base vacuum to 2 × 10
-3more than Pa.
The present invention performs the operation of taking out base vacuum again, because inventor finds in the middle of pre-sputtering process in long-term process of the test, along with the rising of temperature, a small amount of steam and foreign gas is there will be in vacuum chamber, these steam and foreign gas can affect follow-up magnetron sputtering, affect the quality of thin-film solar cells, reduce absorptivity, therefore, again perform the operation of taking out base vacuum, can further improve thin-film solar cells absorptivity, can further improve cell photoelectric conversion efficiency, this is the important discovery of the present invention one and innovative point.
E, again unlatching argon inlet valve pass into argon gas, when vacuum house vacuum degree reaches 2 ~ 9 × 10
-1after Pa, the shielding power supply opening SnS target prepares SnS film, controls power density 100 ~ 300W/cm
2, sputtering time 10 ~ 30 minutes, film thickness 50 ~ 80nm; Prepare ZnS film after SnS film preparation completes, control power density 200 ~ 350W/cm
2, sputtering time 10 ~ 30 minutes, film thickness 50 ~ 80nm.
The main purpose of this step is on FTO glass surface, prepare first segment P-N junction bilayer film, and in this step, vacuum degree is too high or too low all cannot form glow discharging process, and vacuum degree is higher, and the energy of single ion is larger, otherwise then less; Power density is excessive, and target can melt, and cannot perform sputter procedure, too smallly can extend the plated film time, or glow discharge is extinguished, and stops coating process.According to above-mentioned parameter operation, be conducive to that magnetron sputtering process is stable to carry out, be also conducive to finally improving cell light absorptivity.
Prepare the program of SnS film and ZnS film in f, repeated execution of steps e, altogether prepare 2 ~ 4 P-N junction be made up of SnS film and ZnS film.
The object of this process prepares lamination P-N junction film, increases incident photonic absorbance, increase photoelectric conversion efficiency further.
G, P-N junction have prepared rear preparation Al film, control power density 100 ~ 250W/cm
2, sputtering time 10 ~ 15 minutes, sputtering thickness 70 ~ 100nm, namely obtains SnS/ZnS overlapping thin film solar battery after Al film preparation completes.The effect of Al film is the negative pole as battery.
Below by embodiment, the specific embodiment of the present invention is described further, but not therefore by protection scope of the present invention restriction in one embodiment.
The preparation of embodiment one thin-film solar cells of the present invention and effect
Using the FTO electro-conductive glass (SnO of doped with fluorine as substrate
2transparent conducting glass) be clean under Ultrasonic Conditions respectively with deionized water, acetone, absolute ethyl alcohol successively, cleaned and loaded on magnetron sputter substrate holder fixing, FTO face, towards target stand direction, installs rear unlatching substrate baffle plate.
Door for vacuum chamber is closed after magnetron sputter is installed SnS target, ZnS target and Al target.
Unlatching vacuum-pumping system vacuumizes, and makes background vacuum reach 2 × 10
-3more than Pa, removes the foreign gas in vacuum chamber and steam.
Open argon inlet valve, pass into argon gas, in vacuum chamber, vacuum degree reaches 2 × 10
-1during Pa, open all target as sputter power supplys and perform pre-sputtering program, pre-sputtering program setting for from build-up of luminance to the setting power time be 10 minutes, arriving setting power is maintenance 30 minutes, makes target reach operating state.
After pre-sputtering EP (end of program), close all target power supplys, close argon inlet valve, be evacuated to 2 × 10
-3more than Pa vacuum degree, again performs and takes out base vacuum, extracts out when performing pre-sputtering program because temperature raises the steam causing overflowing.
Open argon inlet valve, pass into argon gas, when vacuum house vacuum degree reaches 2 × 10
-1after Pa, close matrix baffle plate, open the shielding power supply of SnS target, preparation SnS film, power density 100W/CM
2, 10 minutes time, thickness 50nm; After prepared by SnS, close the shielding power supply of SnS target, matrix is adjusted to ZnS target opposite side, starts to prepare ZnS film, power density 200W/CM
2, 10 minutes time, thickness 50nm;
Re-execute once above-mentioned preparation SnS membrane process and ZnS membrane process, prepare two P-N junction be made up of SnS film and ZnS film.
Matrix is adjusted to Al target opposite side, preparation Al film, power density 100W/CM
2, 10 minutes time, thickness 70nm.
After whole process completes, on FTO electro-conductive glass substrate, namely plate the lamination ZnS/SnS thin-film solar cells comprising two ZnS/SnS film P-N junction, one deck back electrode Al film, be labeled as sample 1.
For doing photonic absorption experiment, the present embodiment prepares two not containing the sample of Al film simultaneously, is labeled as sample 2, sample 3, and 1 ZnS/SnSP-N knot only prepared by sample 2, and 2 ZnS/SnSP-N knots prepared by sample 3.
Square resistance instrument is adopted to test Al film surface corner and middle square resistance, film inhomogeneities is characterized by square resistance difference, result shows: square resistance is respectively 0.54,0.54,0.54,0.54,0.53, inhomogeneities=[(0.54-0.53)/(0.54+0.53)] × 100%=1.03%, illustrates that film that this programme plates has excellent homogeneity.
Adhesive tape is adhered to film edge placement and centre position respectively, is firmly shut down by adhesive tape after gluing, repeat 10 times respectively, film does not come off from matrix surface, illustrates that film that this programme plates and matrix surface have good combination power.
Be the flat transmitance in 300nm-900nm interval at wavelength with spectrophotometer test sample 2, sample 3, it is 20% that result shows sample 2 transmitance comprising 1 P-N junction, be 5% containing 2 P-N junction sample 3 transmitances, namely the absorptivity of 2 laminations is higher than single p-n junction battery absorptivity.
The preparation of embodiment two thin-film solar cells of the present invention and effect
First using the FTO electro-conductive glass (SnO of doped with fluorine as substrate
2transparent conducting glass) be clean under Ultrasonic Conditions respectively with deionized water, acetone, absolute ethyl alcohol, clean to load on magnetron sputter substrate holder and fixed, FTO face is towards target stand direction, install rear unlatching substrate baffle plate, this step is the impurity in order to remove matrix surface, after improving plated film, the adhesion of film and matrix, prevents film from coming off from matrix surface.
Door for vacuum chamber is closed after magnetron sputter is installed SnS target, ZnS target and Al target.
Unlatching vacuum-pumping system vacuumizes, and makes background vacuum reach 2 × 10
-3more than Pa, removes the foreign gas in vacuum chamber and steam.
Open argon inlet valve, pass into argon gas, in vacuum chamber, vacuum degree reaches 2 × 10
-1during Pa, open all target as sputter power supplys and perform pre-sputtering program, pre-sputtering program setting for from build-up of luminance to the setting power time be 10 minutes, arriving setting power is maintenance 30 minutes, makes target reach operating state.
After pre-sputtering EP (end of program), close all target power supplys, close argon inlet valve, be evacuated to 2 × 10
-3more than Pa vacuum degree, again performs and takes out base vacuum, extracts out when performing pre-sputtering program because temperature raises the steam causing overflowing.
Open argon inlet valve, pass into argon gas, when vacuum house vacuum degree reaches 2 × 10
-1after, close matrix baffle plate, open the shielding power supply of SnS target, preparation SnS film, power density 300CM
2, 10 minutes time, thickness 60nm; After prepared by SnS, close the shielding power supply of SnS target, matrix is adjusted to ZnS target opposite side, starts to prepare ZnS film, power density 350W/CM
2, 10 minutes time, thickness 70nm.
Re-execute above-mentioned preparation SnS membrane process and ZnS membrane process, prepare three P-N junction be made up of SnS film and ZnS film.
Matrix is adjusted to Al target opposite side, starts to prepare Al film, power density 250W/CM
2, 10 minutes time, thickness 80nm
After whole process completes, on FTO electro-conductive glass substrate, namely plate the lamination ZnS/SnS thin-film solar cells comprising three ZnS/SnS film P-N junction, one deck back electrode Al film, be labeled as sample 4.
For doing photonic absorption experiment, the present embodiment prepares two not containing the sample of Al film simultaneously, is labeled as sample 5, sample 6, and 1 ZnS/SnSP-N knot only prepared by sample 5, and 3 ZnS/SnSP-N knots prepared by sample 6, other parameter constant.
After film preparation completes, square resistance instrument is adopted to test sample 4Al film surface corner and middle square resistance, film inhomogeneities is characterized by square resistance difference, result shows: square resistance is respectively 0.49,0.49,0.49,0.49,0.48, inhomogeneities=[(0.49-0.48)/(0.49+0.48)] × 100%=1.04%, illustrates that film that this programme plates has excellent homogeneity.
Adhere to sample 4 film edge placement and centre position respectively with adhesive tape, firmly shut down by adhesive tape after gluing, repeat 10 times respectively, film does not come off from matrix surface, illustrates that film that this programme plates and matrix surface have good combination power.
Be the flat transmitance in 300nm-900nm interval at wavelength with spectrophotometer test sample 5, sample 6, it is 18.3% that result shows sample 5 transmitance comprising 1 P-N junction, be 2.7% containing 3 P-N junction sample 6 transmitances, namely the absorptivity of 3 laminations is higher than single p-n junction and two P-N junction battery absorptivity.
Comparative example one adopts evaporation coating mode to prepare SnS/ZnS overlapping thin film solar battery
Prepared by evaporation coating:
Single p-n junction SnS/ZnS film is prepared according to application number 201010527964.3 " method of ZnS/SnS bilayer film is prepared in vacuum evaporation " described method, and by evaporation simple substance Al at P-N junction plated surface one deck Al film, Al film thickness is 70nm, and matrix specification is that 5CM × 5CM is labeled as sample 7.
Adopt embodiment one method to prepare single p-n junction SnS/ZnS film and Al film, film thickness method of evaporating is consistent, and matrix specification is that 5CM × 5CM is labeled as sample 8.
Square resistance instrument is adopted to test sample 7 and sample 8Al film surface corner and middle square resistance, film inhomogeneities is characterized by square resistance difference, result shows: sample 7 square resistance is respectively 0.56, 0.57, 0.55, 0.54, 0.55, inhomogeneities=[(0.57-0.54)/(0.57+0.54)] × 100%=2.7%, sample 8 square resistance is respectively 0.54, 0.54, 0.54, 0.54, 0.53, inhomogeneities=[(0.54-0.53)/(0.54+0.53)] × 100%=1.03%, illustrate this programme comparatively film that evaporation measure plates there is better uniformity.Can reasonable inferences, the solid matter source due to vacuum vapor deposition method is point source, and when the area of matrix increases, its uniformity will become poorer, and magnetron sputtering method can accomplish planar source, and the degree of uniformity variation will far below vacuum vapor deposition method.
Sample 7 and sample 8 film edge placement and centre position is adhered to respectively with adhesive tape, firmly shut down by adhesive tape after gluing, repeat 10 times respectively, sample 8 film does not come off from matrix surface, and sample 7 edge film separation, illustrate this programme comparatively evaporation measure there is better film-substrate cohesion.
Comparative example two step with embodiment one, but takes out the step of base vacuum again
4 samples 9, sample 10 is prepared according to method described in above-described embodiment one, sample 11, sample 12, wherein sample 9,10 does not plate Al, plating Al sample for what do not comprise that second time takes out base vacuum process, and what sample 11, sample 12 comprised that second time takes out base vacuum process does not plate Al, plating Al sample.
From color, sample 10 surface is partially dark, good not as sample 12 glossiness.
Have some black splotches, sample 11, sample 12 do not have.
Sample 9 light transmission rate is apparently higher than sample 11, and namely sample 9 absorptivity is lower than sample 11.
Adopt step instrument to test to the film thickness of 4 samples, sample 9, sample 10 thickness are respectively: 195nm, 273nm, and sample 11, sample 12 thickness are respectively: 135nm, 180nm.
Adopt square resistance instrument according to method test described in embodiment one, sample 9 square resistance is respectively 0.71,0.71,0.72,0.71,0.69, and sample 10 square resistance is still 0.54,0.54,0.54,0.54,0.53.
Analyze through inventor, cause the reason of above difference to be, under second time does not take out base vacuum process condition, because pre-sputtering program makes vacuum indoor temperature rise, cause the impurity of vacuum-chamber wall and edge absorption and steam to overflow.The spilling of foreign gas and steam, first changes the atmosphere in vacuum chamber, and these component portion enter rete, and film composition is changed, and namely the spot that sample 9, sample 10 film surface occur is the performance that film composition local changes; The change of atmosphere simultaneously causes sputtering yield to decline, and in the same time, the film thickness of sputtering is thinner, causes light absorption to decline, the quality problems such as square resistance rising.
Claims (2)
1.SnS/ZnS overlapping thin film solar battery preparation method, is characterized in that comprising the steps:
A, the FTO electro-conductive glass as substrate to be cleaned up, be installed on magnetron sputter substrate holder; And then close magnetron sputter door for vacuum chamber after SnS target, ZnS target and Al target are installed;
B, unlatching vacuum-pumping system vacuumize, and make background vacuum reach 2 × 10
-3more than Pa;
C, unlatching argon inlet valve pass into argon gas, make vacuum degree in vacuum chamber reach 2 × 10
-1during Pa, open all target as sputter power supplys and perform pre-sputtering program; Pre-sputtering program setting for from build-up of luminance to the setting power time be 10 minutes, arrive after setting power and maintain 30 minutes;
After d, pre-sputtering EP (end of program), close all target power supplys, close argon inlet valve, again take out base vacuum to 2 × 10
-3more than Pa;
E, again unlatching argon inlet valve pass into argon gas, when vacuum house vacuum degree reaches 2 ~ 9 × 10
-1after Pa, the shielding power supply opening SnS target prepares SnS film, controls power density 100 ~ 300W/cm
2, sputtering time 10 ~ 30 minutes, film thickness 50 ~ 80nm; Prepare ZnS film after SnS film preparation completes, control power density 200 ~ 350W/cm
2, sputtering time 10 ~ 30 minutes, film thickness 50 ~ 80nm;
Prepare the program of SnS film and ZnS film in f, repeated execution of steps e, altogether prepare 2 ~ 4 P-N junction be made up of SnS film and ZnS film;
G, P-N junction have prepared rear preparation Al film, control power density 100 ~ 250W/cm
2, sputtering time 10 ~ 15 minutes, sputtering thickness 70 ~ 100nm, namely obtains SnS/ZnS overlapping thin film solar battery after Al film preparation completes.
2. SnS/ZnS overlapping thin film solar battery preparation method according to claim 1, is characterized in that: in step a, and the cleaning of FTO electro-conductive glass is cleaned under Ultrasonic Conditions with deionized water, acetone, absolute ethyl alcohol successively.
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| CN111254402B (en) * | 2020-03-11 | 2021-11-26 | 鄂尔多斯应用技术学院 | Intermediate belt film of Cr-doped ZnS and preparation method thereof |
| CN111682079B (en) * | 2020-06-01 | 2021-12-14 | 大连理工大学 | Medium/far infrared transparent conductive material system and method for preparing conductive film by using same |
| JP2022003675A (en) * | 2020-06-23 | 2022-01-11 | 国立大学法人東北大学 | N type sns thin film, photoelectric conversion element, solar cell, method for manufacturing n type sns thin film and n type sns thin film manufacturing apparatus |
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